Dinitrogen Activation and Transformation Promoted by Rare Earth and Actinide Complexes

Chen, Xiao; Xu, Hanhua; Shi, Xianghui; Wei, Junnian; Xi, Zhenfeng

doi:10.6023/a22060253

Cited by 8 publications

(4 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Our group has been dedicated to developing novel ligands for small molecule activation. − Recently, we have designed and synthesized an N -aryloxide-amidine ligand ( 1 ), [ONNO] ligand, connecting phenoxide (PhO – ) ligands with amidine and alkyl (CH 2 ) linkers. , This work led to the synthesis of distinctive organometallic complexes with group 4 metals, where the [ONNO] ligand featured flexibility in coordination. Given the diverse coordination potential of amidine ligands − and the similarities between hafnium and thorium, ,,− we are now exploring the application of our N -aryloxide-amidine ligand in thorium chemistry.…”

Section: Introductionmentioning

confidence: 99%

N-Aryloxide-Amidinate Thorium Complexes

Xu,

Lv,

Chen

et al. 2024

Inorg. Chem.

Self Cite

View full text Add to dashboard Cite

An N-aryloxide-amidine ligand (1), [ONNO] ligand, integrating phenoxide (PhO − ) and amidine ligands through methylene linkers, was employed in actinide chemistry. Upon reaction of the deprotonated ligand with ThCl 4 (DME) 2 in ether, the corresponding dimer complex 2 was obtained. Upon treatment of 2 with KCp* (Cp* = Cp(Me) 5 ) in tetrahydrofuran, the corresponding {[ONNO]Th IV Cp*-(LiCl)} 2 (4) was obtained. In complex 2, the two ArO − arms bonded from the same ligand to different Th IV centers. In contrast, both ArO − arms coordinated to the same metal center in 4. Notably, when a mixture of 2 and bipyridine was treated with one or two equiv of KC 8 , the [ONNO]Th IV -bipyridyl• ̅ radical dimer complex (5) and [ONNO]Th IV -bipyridyl 2− dianionic dimer species (6) were obtained, respectively.

show abstract

Section: Introductionmentioning

confidence: 99%

N-Aryloxide-Amidinate Thorium Complexes

Xu,

Lv,

Chen

et al. 2024

Inorg. Chem.

Self Cite

View full text Add to dashboard Cite

show abstract

“…This ammonia synthesis process consumes 1%—2% of the world's annual energy supply along with the huge CO 2 emission. [ 10‐13 ] Hence, a variety of strategies have been developed to achieve dinitrogen reduction more efficiently and in an environmentally‐friendly manner. [ 14‐37 ]…”

Section: Introductionmentioning

confidence: 99%

Light‐Driven Dinitrogen Activation with Transition Metal Complexes: Mechanisms and Applications^†

Zhao

Wei

2023

Chin. J. Chem.

Self Cite

View full text Add to dashboard Cite

Comprehensive SummaryThe Haber‐Bosch process, which is used for ammonia (NH3) synthesis, requires vast amounts of energy, accounting for approximately 1%—2% of the world's annual energy consumption. Therefore, researchers in both industry and academia are interested in developing sustainable and environmentally friendly methods for synthesizing nitrogenous compounds at ambient conditions using renewable energy sources such as visible light. While several examples of thermal activation of dinitrogen molecules have been demonstrated using various transition metals and ligand frameworks, the use of light to weaken or split the strong N—N bond has been less explored. This article presents an overview of molecular complexes capable of dinitrogen photocleavage and provides mechanistic insights into the photoactivation process through experimental and theoretical studies. We believe this review will provide readers with an in‐depth understanding of the current state‐of‐the‐art and future research perspectives, particularly in the use of visible light for dinitrogen activation and transformation.

show abstract

“…Since the first dinitrogen complex was prepared in 1965 by Allen and Senoff, the activation of N 2 with transition metals has captivated the interest of chemists. A plethora of transition-metal–dinitrogen complexes (TM–N 2 ) have been synthesized, demonstrating a variety of binding modes. − Among them, the bridging (μ–η 1 : η 1 -N 2 ) end-on M1–N 2 –M2 complexes stand out due to their typical coordination mode. − However, despite the progress made in their syntheses, these complexes pose a significant challenge in terms of further N 2 derivatization. − So far, the studies of N 2 -bridged end-on M1–N 2 –M2 binuclear complexes have primarily concentrated on homobimetallic compounds, leaving the heterobimetallic M1–N 2 –M2 complexes relatively unexplored and insufficiently characterized. − ,− Nonetheless, these heterobimetallic N 2 complexes present a fascinating opportunity: the potential to induce the polarization of nonpolar N 2 gas, which might facilitate subsequent N 2 derivatization reactions. Therefore, research on heterobimetallic dinitrogen complexes is necessary and holds promise for unveiling novel possibilities in the field of N 2 activation.…”

Section: Introductionmentioning

confidence: 99%

Syntheses and Characterizations of Hetero-Bimetallic Chromium-Dinitrogen Transition-Metal Complexes

Wang,

et al. 2023

Inorg. Chem.

Self Cite

View full text Add to dashboard Cite

In the domain of N2 activation, hetero-bimetallic dinitrogen complexes are garnering substantial interest due to their potential to induce polarization in nonpolar N2 gas. Herein, we present the syntheses and characterizations of three novel hetero-multimetallic dinitrogen complexes: Cp*Cr(depe)N2V(depe) Me [O, P, O] 5, Cp*Cr(depe)N2V(depe) Tipp [O, P, O] 6, and [Cp*Cr(depe)N2]2Ti Tipp [O, P, O] 7. These complexes were synthesized via a transmetalation process involving the treatment of [Cr0–N2]− complex 4 with vanadium and titanium chloride complexes bearing alkyl or aryl substituted bis(o-hydroxyphenyl)-phenyl phosphine R [O, P, O] ligand (alkyl = methyl, aryl = 2,4,6-tri-isopropylbenzene). X-ray analysis shows that complexes 5 and 6 exhibit heterodinuclear structures, while complex 7 exhibits a heterotrinuclear core with two N2 ligands concurrently coordinated to two chromium and one titanium atoms. Raman spectroscopic data show that the N–N stretching vibration of the N2 moiety is clearly downshifted relative to free N2 and to mononuclear [Cr0–N2]− complex 4.

show abstract

Dinitrogen Activation and Transformation Promoted by Rare Earth and Actinide Complexes

Cited by 8 publications

References 0 publications

N-Aryloxide-Amidinate Thorium Complexes

N-Aryloxide-Amidinate Thorium Complexes

Light‐Driven Dinitrogen Activation with Transition Metal Complexes: Mechanisms and Applications^†

Syntheses and Characterizations of Hetero-Bimetallic Chromium-Dinitrogen Transition-Metal Complexes

Contact Info

Product

Resources

About

Dinitrogen Activation and Transformation Promoted by Rare Earth and Actinide Complexes

Cited by 8 publications

References 0 publications

N-Aryloxide-Amidinate Thorium Complexes

N-Aryloxide-Amidinate Thorium Complexes

Light‐Driven Dinitrogen Activation with Transition Metal Complexes: Mechanisms and Applications†

Syntheses and Characterizations of Hetero-Bimetallic Chromium-Dinitrogen Transition-Metal Complexes

Contact Info

Product

Resources

About

Light‐Driven Dinitrogen Activation with Transition Metal Complexes: Mechanisms and Applications^†